Sulphonylurea and/adjuvant based solid mixtures

ABSTRACT

Solid mixtures comprisinga) an active ingredient from the group of the sulfonylureas andb) a sulfate- or sulfonate-containing surfactant.

This application is a 371 of PCT/EP98/00413 filed on Feb. 4, 1998.

The present invention relates to solid mixtures based on sulfonylureasand adjuvants.

Sulfonylureas (termed “SU” hereinafter) are a group of highly activeherbicides which are used widely in crop protection.

Due to the mechanism of active ingredient uptake via the leaf, it ispossible to improve the activity of SU by adding surface-activesubstances such as wetters to the spray mixture (cf. Green et al.,ANPP,Seizieme conference du columa—Journees internationales sur la luttecontre les mauvaises herbes 1995, pp. 469-474; “DPX-KG 691—A newsurfactant for sulfonylurea herbicides”).

Substances which are described in the literature as being particularlysuitable wetters are, inter alia, oil adjuvants (Nalejewa et al., WeedTechnol. 1995, 9, pp. 689-695) or alcohol ethoxylates (see above andDunne et al., Weed Science 1994, 42, pp. 82-85; Green, Weed Technol.1993, 7, pp. 633-640). In agricultural practice, these substances areadded to the spray mixture by the practitioner in the form of tank mixadditives. The mixture of SU herbicide and surfactant is prepared in thespray tank a short time prior to use.

An example of a commercially available product is a twin pack with thetrade name CATO® (Du Pont de Nemours), which is composed ofwater-dipersible granules in which the active ingredient rimsulfuron(component A) amounts to 25%, and of a wetter (component B) packagedseparately and composed of a mixture of 2-butoxyethanol, polyethoxylatedtallow amine and nonylphenyl polyethylene glycol ether. For use, the twocomponents are mixed in the spray tank as described above.

Under practice conditions, it would be desirable to be able to employfinished formulations which already comprise an activity-enhancingwetter, so as to avoid mixing immediately prior to use, which isproblematic. This would allow logistics problems and mixing errors to beavoided when making the spray mixture. Moreover, solid formulations aregenerally advantageous, from the point of view of application, as far asdesigning and disposing of the packaging is concerned.

The literature furthermore discloses that formulations which comprisesulfonlyureas are problematic with regard to active ingredientstability, since the active ingredient may undergo decomposition in thecourse of time when the conditions are unfavorable. If this happens, thedesired herbicidal activity is lost. The tendency to decomposition isalso a problem with regard to the registration requirements, since thestability of PS-type active ingredients in formulations must meetcertain minimum requirements upon registration.

JP-A 62/084004 describes the use of calcium carbonate and sodiumtripolyphosphate for stabilizing SU-containing formulations.

JP-A 63/023806 describes how this problem can be solved by usingspecific carriers and vegetable oils for the preparation of solidSU-containing formulations. JP-A 08/104603 describes similar effectswhen using epoxidized natural oils. The two applications mentioned aboveshare the feature of incorporating vegetable oils into the solidformulation in order to exploit not only an improved stability, but alsothe activity-enhancing effects of these substances, which act asadjuvants.

Similar effects are exploited, (cf. EP-A 313317 and EP-A 554015) whenincorporating vegetable oils into liquid formulations (as a rule,suspension concentrates.

It is also known from the prior art to use sulfate- orsulfonate-containing surfactants as wetters/adjuvants.

EP-A 378 895 and W092/12637 describe sulfate- or sulfonate-containingsurfactants together with the active ingredient N-phosphonomethylglycinein solid formulations.

EP-A 413 267 describes the use of sulfate- or sulfonate-containingsurfactants together with the active ingredients glufosinate-ammoniumand fenoxaprop-ethyl.

It is an object of the present invention to provide solid formulationswith sulfonylureas as active ingredients which comprise adjuvants in thesolid formulation itself and which are superior to prior-art solidformulations.

We have found that this object is achieved by solid mixtures whichcomprise

a) a sulfonylurea and

b) an adjuvant from the group of the sulfate- or sulfonate-containingsurfactants.

Surprisingly, it has been found that the use of sulfate- orsulfonate-containing surfactants as wetters in SU-containing solidformulations results in a pronounced stabilization of the activeingredient in comparison with other wetters (e.g. ethoxylated fattyamines or alcohol ethoxylates). This effect can be observed mainly whenwater-soluble inorganic salts, such as ammonium sulfate or potassiumsulfate, are present in addition to herbicidally active ingredients. Thestabilizing effect is particularly pronounced when the wetter isemployed at the concentration required for the biological action.

Storage-stable finished formulations with good biological activity canbe obtained by mixing the SU with other active ingredients, sulfate- orsulfonate-containing surfactants and ammonium sulfate.

We have furthermore found processes for the preparation of the solidmixtures according to the invention and their use as crop protectioncompositions for controlling undesirable harmful plants.

Suitable sulfonylureas a) are generally compounds which have thestructural unit

Preferred SU are those of the following structures I:

where J has the following meanings:

where the substituents R to R¹⁸ have the following meanings:

R is H or CH₃;

R¹ is F, Cl, Br, NO₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₄-cycloalkyl,C₂-C₄-haloalkenyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₂-C₄-alkoxyalkoxy,CO₂R¹², C(O)NR¹³R¹⁴, SO₂NR¹⁵R¹⁶, S(O)_(n)R¹⁷, C(O)R¹⁸, CH₂CN or L;

R² is H, F, Cl, Br, CN, CH₃, OCH₃, SCH₃, CF₃ or OCF₂H;

R³ is Cl, NO₂, CO₂CH₃, CO₂CH₂CH₃, SO₂N(CH₃)₂, SO₂CH₃, SO₂CH₂CH₃, OCH₃ orOCH₂CH₃;

R⁴ is C₁-C₃-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₂-C₄-haloalkenyl, F,Cl, Br, NO₂, CO₂R¹², C(O)NR¹³R¹⁴, SO₂NR¹⁵R¹⁶, S(O)_(n)R¹⁷, C(O)R¹⁸ or L;

R⁵ is H, F, Cl, Br or CH₃;

R⁶ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₄-haloalkenyl, F, Cl, Br, CO₂R¹²,C(O)NR¹³R^(14,) SO₂NR¹⁵R¹⁶, S(O)_(n)R¹⁷, C(O)R¹⁸ or L;

R⁷ is H, F, Cl, CH₃ or CF₃;

R⁸ is H, C₁-C₄-alkyl or pyridyl;

R⁹ is C₁-C₄-alkyl, C₁-C₄-alkoxy, F, Cl, Br, NO₂, CO₂R¹², SO₂NR¹⁵R¹⁶S(O)_(n)R¹⁷, OCF₂H, C(O)R¹⁸, C₂-C₄-haloalkenyl or L;

R¹⁰ is H, Cl, F, Br, C₁-C₄-alkyl or C₁-C₄-alkoxy;

R¹¹ is H, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₄-alkoxy, haloalkenyl, F, Cl,Br, CO₂R¹², C(O)NR¹³R¹⁴, SO₂NR¹⁵R¹⁶, S(O)_(n)R¹⁷, C(O)R¹⁸ or L;

R¹² is C₁-C₄-alkyl, unsubstituted or substituted by halogen,C₁-C₄-alkoxy or CN, allyl or propargyl;

R¹³ is H, C₁-C₄-alkyl or C₁-C₄-alkoxy;

R¹⁴ is C₁-C₄-alkyl;

R¹⁵ is H, C₁-C₄-alkyl, C₁-C₄-alkoxy, allyl or cyclopropyl;

R¹⁶ is H or C₁-C₄-alkyl;

R¹⁷ is C₁-C₄-alkyl, C₁-C₄-haloalkyl, allyl or propargyl;

R¹⁸ is C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₃-C₅-cycloalkyl, unsubstitutedor substituted by halogen;

is 0, 1 or 2;

L has the structure II

 where

R_(j) is H or C₁-C₃-alkyl;

W is O or S;

X is H, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-haloalkyl,C₁-C₄-haloalkylthio, C₁-C₄-alkylthio, halogen, C₂-C₅-alkoxyalkyl,C₂-C₅-alkoxyalkoxy, amino, C₁-C₃-alkylamino or di(C₁-C₃-alkyl)amino;

Y is H, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-haloalkylthio, C₂-C₅-alkoxyalkyl, C₂-C₅-alkoxyalkoxy, amino,C₁-C₃-alkylamino, di(C₁-C₃-alkyl)amino, C₃-C₄-alkenyloxy,C₃-C₄-alkanyloxy, C₂-C₅-alkylthioalkyl, C₂-C₅-alkylsulfinylalkyl,C₂-C₅-alkylsulfonylalkyl, C₁-C₄-haloalkyl, C₂-C₄-alkenyl,C₃-C₅-cycloalkyl, azido, fluorine or cyano;

Z is CH or N,

and the agriculturally useful salts thereof.

Some suitable SU together with their INN (International NonproprietaryName) in accordance with Pesticide Manual may be mentioned below:

ACC 322140;

amidosulfuron;

azimsulfuron(N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]-carbonyl]-1-methyl-4-(2-methyl-2H-tetrazol-5-yl)-1H-pyrazole-5-sulfonamide);

bensulfuron-methyl (methyl2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)-amino]-carbonyl]amino]sulfonyl]methyl]benzoate);

ethyl2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)-amino]carbonyl]amino]sulfonyl]benzoate(chlorimuron-ethyl);2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]-carbonyl]benzenesulfonamide(chlorosulfuron);

chlorosulfoxim;

cinosulfuron;

cyclosulfamuron;

ethametsulfuron-methyl (methyl2-[[[[[4-ethoxy-6-(methylamino)-1,3,5-triazin-2-yl]amino]carbonyl]amino]sulfonyl]benzoate);

ethoxysulfuron;

fluazasulfuron;

flupyrsulfuron (methyl2-[[[[(4,6-dimethoxy-2-pyrimidinyl)-amino]carbonyl]amino]sulfonyl]-6-(trifluoromethyl)-3-pyridinecarboxylate);

halosulfuron-methyl

imazosulfuron;

methyl2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]-carbonyl]amino]sulfonyl]benzoate(metsulfuron-methyl);

nicosulfuron(2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]-carbonyl]amino]sulfonyl]-N,N-dimethyl-3-pyridinecarboxamide);oxasulfuron;

primisulfuron (methyl2-[[[[[4,6-bis(difluoromethoxy)-2-pyrimidinyl]amino]carbonyl]amino]sulfonyl]benzoate);prosulfuron;

pyrazosulfuron-ethyl (ethyl5-[[[[(4,6-dimethoxy-2-pyrimidinyl)-amino]carbonyl]amino]sulfonyl]-1-methyl-1H-pyrazole-4-carboxylate);

rimsulfuron(N-[[(4,6-dimethoxy-2-pyrimidinylamino]carbonyl]-3-(ethylsulfonyl)-2-pyridinesulfonamide);sulfosulfuron;

sulfometuron-methyl (methyl2-[[[[(4,6-dimethyl-2-pyrimidinyl)-amino]carbonyl]amino]sulfonyl]benzoate);

thifensulfuron-methyl(methyl-3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophene-carboxylate);

2-(2-chloroethoxy)-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]carbonyl]benzenesulfonamide(triasulfuron);

tribenuron-methyl (methyl2-[[[[N-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-N-methylamino]carbonyl]amino]sulfonyl]benzoate);and

triflusulfuron-methyl (Methyl2-[[[[[4-(dimethylamino)-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]amino]carbonyl]-amino]sulfonyl]-3-methylbenzoate).

Especially preferred are sulfonylureas of the formula III (whichcorresponds to the formula I where J=J₁), as are disclosed in, forexample, EP-A 388 873, EP-A 559 814, EP-A 291 851 and EP-A 446 743:

where the substituents have the following meanings:

R¹ is C₁-C₄-alkyl which can have attached to it one to five of thefollowing groups: methoxy, ethoxy, SO₂CH₃, cyano, chlorine, fluorine,SCH₃, S(O)CH₃;

halogen;

a group ER¹⁹ where E is O, S or NR²⁰;

COOR¹²;

NO₂;

S(O)_(n)R¹⁷, SO₂NR¹⁵R¹⁶, CONR¹³R¹⁴;

R² is hydrogen, methyl, halogen, methoxy, nitro, cyano, trifluoromethyl,trifluoromethoxy, difluoromethoxy or methylthio,

Y is F, CF₃, CF₂Cl, CF₂H, OCF₃, OCF₂Cl, C₁-C₄-alkyl or C₁-C₄-alkoxy;

X is C₁-C₂-alkoxy, C₁-C₂-alkyl, C₁-C₂-alkylthio, C₁-C₂-alkylamino,di-C₁-C₂-alkylamino, halogen, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy,

R is hydrogen or methyl;

R¹⁹ is C₁-C₄-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl or C₃-C₆-cycloalkyl,which can have attached to them 1 to 5 halogen atoms; furthermore in theevent that E is O or NR²⁰, R¹⁹ is also methylsulfonyl, ethylsulfonyl,trifluoromethylsulfonyl, allylsulfonyl, propargylsulfonyl ordimethylsulfamoyl;

R²⁰ is hydrogen, methyl or ethyl;

R¹² is a C₁-C₄-alkyl group, which can have attached to it up to three ofthe following radicals: halogen, C₁-C₄-alkoxy, allyl or propargyl;

R¹⁷ is a C₁-C₄-alkyl group, which can have attached to it one to threeof the following radicals: halogen, C₁-C₄-alkoxy, allyl or propargyl;

R¹⁵ is hydrogen, a C₁-C₂-alkoxy group or a C₁-C₄-alkyl group;

R¹⁶ is hydrogen or a C₁-C₄-alkyl group;

n is 1 or 2 and

Z is N or CH.

Particularly preferred sulfonylureas of the formula III are those of theformula I where J is J₁ and the rest of the substituents have thefollowing meanings:

R¹ is CO₂CH₃, CO₂C₂H₅, CO₂iC₃H₇, CF₃, CF₂H, OSO₂CH₃, OSO₂N(CH₃)₂, Cl,NO₂, SO₂N(CH₃)₂, SO₂CH₃ or N(CH₃)SO₂CH₃,

R² is hydrogen, Cl, F or C₁-C₂-alkyl,

Y is CF₂H, OCF₃, OCF₂Cl, CF₂Cl, CF₃ or F,

X is OCH₃, OC₂H₅, OCF₃, OCF₂Cl, CF₃, Cl, F, NH(CH₃), N(CH₃)₂ orC₁-C₂-alkyl,

R⁵ is hydrogen and

Z is N or CH.

Very especially preferred compounds of the formula III are compiled inthe table which follows.

TABLE (III)

No. R¹ R² R Y X Z  1 CO₂CH₃ H H OCF₂Cl OCH₃ CH  2 CO₂C₂H₅ H H OCF₂ClOCH₃ CH  3 CO₂iC₃H₇ H H OCF₂Cl OCH₃ CH  4 NO₂ H H OCF₂Cl OCH₃ CH  5SO₂CH₃ H H OCF₂Cl OCH₃ CH  6 SO₂N(CH₃)₂ H H OCF₂Cl OCH₃ CH  7 Cl H HOCF₂Cl OCH₃ CH  8 N(CH₃)SO₂CH₃ H H OCF₂Cl OCH₃ CH  9 OSO₂CH₃ H H OCF₂ClOCH₃ CH  10 OSO₂N(CH₃)₂ H H OCF₂Cl OCH₃ CH  11 CF₃ H H OCF₂Cl OCH₃ CH 12 CF₂H H H OCF₂Cl OCH₃ CH  13 CO₂CH₃ H H OCF₃ OCH₃ CH  14 CO₂C₂H₅ H HOCF₃ OCH₃ CH  15 CO₂iC₃H₇ H H OCF₃ OCH₃ CH  16 NO₂ H H OCF₃ OCH₃ CH  17SO₂CH₃ H H OCF₃ OCH₃ CH  18 SO₂N(CH₃)₂ H H OCF₃ OCH₃ CH  19 Cl H H OCF₃OCH₃ CH  20 N(CH₃)SO₂CH₃ H H OCF₃ OCH₃ CH  21 OSO₂CH₃ H H OCF₃ OCH₃ CH 22 OSO₂N(CH₃)₂ H H OCF₃ OCH₃ CH  23 CF₃ H H OCF₃ OCH₃ CH  24 CF₂H H HOCF₃ OCH₃ CH  25 CO₂CH₃ H H F OCH₃ CH  26 CO₂C₂H₅ H H F OCH₃ CH  27CO₂iC₃H₇ H H F OCH₃ CH  28 NO₂ H H F OCH₃ CH  29 SO₂CH₃ H H F OCH₃ CH 30 SO₂N(CH₃)₂ H H F OCH₃ CH  31 Cl H H F OCH₃ CH  32 N(CH₃)SO₂CH₃ H H FOCH₃ CH  33 OSO₂CH₃ H H F OCH₃ CH  34 OSO₂N(CH₃)₂ H H F OCH₃ CH  35 CF₃H H F OCH₃ CH  36 CF₂H H H F OCH₃ CH  37 CO₂CH₃ H H CF₃ OCH₃ N  38CO₂C₂H₅ H H CF₃ OCH₃ N  39 CO₂iC₃H₇ H H CF₃ OCH₃ N  40 NO₂ H H CF₃ OCH₃N  41 SO₂CH₃ H H CF₃ OCH₃ N  42 SO₂N(CH₃)₂ H H CF₃ OCH₃ N  43 Cl H H CF₃OCH₃ N  44 N(CH₃)SO₂CH₃ H H CF₃ OCH₃ N  45 OSO₂CH₃ H H CF₃ OCH₃ N  46OSO₂N(CH₃)₂ H H CF₃ OCH₃ N  47 CF₃ H H CF₃ OCH₃ N  48 CF₂H H H CF₃ OCH₃N  49 CO₂CH₃ H H CF₃ OCH₃ CH  50 CO₂C₂H₅ H H CF₃ OCH₃ CH  51 CO₂iC₃H₇ HH CF₃ OCH₃ CH  52 NO₂ H H CF₃ OCH₃ CH  53 SO₂CH₃ H H CF₃ OCH₃ CH  54SO₂N(CH₃)₂ H H CF₃ OCH₃ CH  55 Cl H H CF₃ OCH₃ CH  56 N(CH₃)SO₂CH₃ H HCF₃ OCH₃ CH  57 OSO₂CH₃ H H CF₃ OCH₃ CH  58 OSO₂N(CH₃)₂ H H CF₃ OCH₃ CH 59 CF₃ H H CF₃ OCH₃ CH  60 CF₂H H H CF₃ OCH₃ CH  61 CO₂CH₃ H H CF₂HOCH₃ N  62 CO₂C₂H₅ H H CF₂H OCH₃ N  63 CO₂iC₃H₇ H H CF₂H OCH₃ N  64 NO₂H H CF₂H OCH₃ N  65 SO₂CH₃ H H CF₂H OCH₃ N  66 SO₂N(CH₃)₂ H H CF₂H OCH₃N  67 Cl H H CF₂H OCH₃ N  68 N(CH₃)SO₂CH₃ H H CF₂H OCH₃ N  69 OSO₂CH₃ HH CF₂H OCH₃ N  70 OSO₂N(CH₃)₂ H H CF₂H OCH₃ N  71 CF₃ H H CF₂H OCH₃ N 72 CF₂H H H CF₂H OCH₃ N  73 CO₂CH₃ H H CF₂H OCH₃ CH  74 CO₂C₂H₅ H HCF₂H OCH₃ CH  75 CO₂iC₃H₇ H H CF₂H OCH₃ CH  76 NO₂ H H CF₂H OCH₃ CH  77SO₂CH₃ H H CF₂H OCH₃ CH  78 SO₂N(CH₃)₂ H H CF₂H OCH₃ CH  79 Cl H H CF₂HOCH₃ CH  80 N(CH₃)SO₂CH₃ H H CF₂H OCH₃ CH  81 OSO₂CH₃ H H CF₂H OCH₃ CH 82 OSO₂N(CH₃)₂ H H CF₂H OCH₃ CH  83 CF₃ H H CF₂H OCH₃ CH  84 CF₂H H HCF₂H OCH₃ CH  85 CO₂CH₃ H H CF₂Cl OCH₃ N  86 CO₂C₂H₅ H H CF₂Cl OCH₃ N 87 CO₂iC₃H₇ H H CF₂Cl OCH₃ N  88 NO₂ H H CF₂Cl OCH₃ N  89 SO₂CH₃ H HCF₂Cl OCH₃ N  90 SO₂N(CH₃)₂ H H CF₂Cl OCH₃ N  91 Cl H H CF₂Cl OCH₃ N  92N(CH₃)SO₂CH₃ H H CF₂Cl OCH₃ N  93 OSO₂CH₃ H H CF₂Cl OCH₃ N  94OSO₂N(CH₃)₂ H H CF₂Cl OCH₃ N  95 CF₃ H H CF₂Cl OCH₃ N  96 CF₂H H H CF₂ClOCH₃ N  97 CO₂CH₃ 3-F H Cl OCH₃ CH  98 CF₂CF₃ H H CH₃ OCH₃ N  99 CF₂CF₃H H CH₃ OCH₃ N 100 SO₂C₂H₅ H H F OCH₃ CH

Naturally, it is also possible to employ mixtures of a number ofsulfonylureas as component a).

The solid formulations according to the invention comprise one or moresulfate- or sulfonate-containing surfactants as component b).

Suitable products are described, for example, in McCutheon's Emulsifiersand Detergents, Volume 1 1994, North American Edition, McCuthesonDivision, Glen Rock, N.J., USA, or in Volume 2 of this publication(International Edition). “Surfactants in Europe”, A Directory of surfaceactive agents available in Europe, 2nd edition, 1989, Terg Data,Darlington, England may also be mentioned.

Substances which may be mentioned by way of example are alkyl sulfates(Texapon®), alkylsulfonates (Lutensit®A-PS, Hostapur® SAS, Witconate®NAS, Texapon®SCO) alkylbenzenesulfonates (Lutensit® ALB-N-BASF,Rhodacal®-American Cyanamid), alpha-olefinsulfonates (Witconates® AOS,Hostapur® OSB), alkyl polyglycol ether sulfonates, alkyl ether sulfates(Witcolate®, Lutensits® A-ES) alkyl polyglycol ether sulfates,polyoxyalkylene alkylaryl ether sulfates, polyoxyalkylene styryl ethersulfates and dialkyl sulfosuccinates (Lutensit® ABO-BASF, Aerosol®OT-American Cyanamid, Emcol® -Witco, Geropon® -Rhone Poulenc) thesodium, potassium and ammonium salts thereof, or mixtures of these.

Especially preferred are alkylsulfonates, paraffinsulfonates andolefinsulfonates, which have attached to them a C₈-C₂₅-, preferably aC₁₀-C₂₀-, alkyl radical. Suitable products are commercially availableunder the names Lutensit® A-PS (BASF AG), Hostapur® SAS 60, Hostapur® OS(both by Hoechst AG), Witconate® NAS 8, Witconate® AOS, Witconate® 3203,Witconate® 1840-X (all by Witco Corporation) or Texapon® SCO (HenkelKGaA).

Component a) generally amounts to from 0.5 to 75% by weight, preferably1 to 25% by weight, in the solid mixtures according to the invention,based on the total weight of the formulation.

The sulfate- or sulfonate-containing surfactants (component b) generallyamount to from 1 to 75, in particular 1 to 50 and especially preferably5 to 25,% by weight, based on the total weight of the formulation.

In addition to components a) and b), the solid mixtures according to theinvention may comprise other active ingredients which are miscible withsulfonylureas or act as synergists together with these. Suitableproducts are known to those skilled in the art and are described in theliterature. The following groups of other active ingredients may bementioned by way of example by their INN:

c1: 1,3,4-thiadiazoles: buthidazoles, cyprazoles;

c2: amides: allidochlor (CDAA), benzoylprop-ethyl, bromobutide,chlorothiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid(benzchlomet), flamprop-methyl, fosamin, isoxaben, monalide, naptalame,pronamid (propyzamid), propanil;

c3: aminophosphoric acids: bilanafos (bialaphos), buminafos,glufosinate-ammonium, glyphosate, sulfosate;

c4: aminotriazoles: amitrol;

c5: anilides: anilofos, mefenacet, thiafluamide;

c6: aryloxyalkanoic acids: 2,4-D, 2,4-DB, clomeprop, dichlorprop,dichlorprop-P, (2,4-DP-P), fenoprop (2,4,5-TP), fluoroxypyr, MCPA, MCPB,mecoprop, mecoprop-P, napropamide, napropanilide, triclopyr;

c7: benzoic acids: chloramben, dicamba;

c8: benzothiadiazinones: bentazone;

c9: bleachers: clomazone (dimethazone), diflufenican, fluorochloridone,flupoxam, fluridone, pyrazolate, sulcotrione (chloro-mesulone)isoxaflutol,2-(2′-chloro-3′-ethoxy-4′-ethylsulfonyl-benzoyl)-4-methylcyclohexane-1,3-dione;

c10: carbamates: asulam, barban, butylate, carbetamide, chlorbufam,chlorpropham, cycloate, desmedipham, di-allate, EPTC, esprocarb,molinate, orbencarb, pebulate, phenisopham, phenmedipham, propham,prosulfocarb, pyributicarb, sulf-allate (CDEC), terbucarb, thiobencarb(benthiocarb), tiocarbazil, tri-allate, vernolate;

c11: quinolinecarboxylic acids: quinclorac, quinmerac;

c12: chloroacetanilides: acetochlor, alachlor, butachlor, butenachlor,diethatyl-ethyl, dimethachlor, dimethenamide (cf. also under categoryc2) metazachlor, metolachlor, pretilachlor, propachlor, prynachlor,terbuchlor, thenylchlor, xylachlor;

c13: cyclohexenones: alloxydim, caloxydim, clethodim, cloproxydim,cycloxydim, sethoxydim, tralkoxydim,2-{1-[2-(4-chlorophenoxy)propyloxy-imino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclo-hexen-1-one;

c14: dichloropropionic acids: dalapon;

c15: dihydrobenzofurans: ethofumesate;

c16: dihydrofuran-1-ones: flurtamone;

c17: dinitroanilines: benefin, butralin, dinitramin, ethalfluralin,fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin,prodiamine, profluralin, trifluralin;

c18: dinitrophenols: bromofenoxim, dinoseb, dinoseb-acetate, dinoterb,DNOC;

c19: diphenyl ethers: acifluorfen-sodium, aclonifen, bifenox,chlornitrofen (CNP), difenoxuron, ethoxyfen, fluorodifen,fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen,nitrofluorfen, oxyfluorfen;

c20: dipyridylenes: cyperquat, difenzoquat-methylsulfate, diquat,paraquat-dichloride;

c21: ureas: benzthiazuron, buturon, chlorbromuron, chioroxuron,chlortoluron, cumyluron, dibenzyluron, cycluron, dimefuron, diuron,dymron, ethidimuron, fenuron, fluormeturon, isoproturon, isouron,karbutilat, linuron, methabenzthiazuron, metobenzuron, metoxuron,monolinuron, monuron, neburon, siduron, tebuthiuron, trimeturon;

c22: imidazoles: isocarbamide;

c23: imidazolinones: imazamethapyr, imazapyr, imazaquin,imazethabenz-methyl (imazame),imazethapyr, imazamox;

c24: oxadiazoles: methazole, oxadiargyl, oxadiazone;

c25: oxiranes: tridiphane;

c26: phenols: bromoxynil, ioxynil;

c27: phenoxypropionic esters: clodinafop, cyhalofop-butyl,diclofop-methyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl,fenthiaprop-ethyl, fluazifop-butyl, fluazifop-p-butyl,haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-p-methyl,isoxapyrifop, propaquizafop, quizalofop-ethyl, guizalofop-p-ethyl,quizalofop-tefuryl;

c28: phenylacetic acids: chlorfenac (fenac);

c29: phenylpropionic acids: chlorophenprop-methyl;

c30: protoporphyrinogen IX oxydase inhibitors: benzofenap,cinidon-ethyl, flumiclorac-pentyl, flumioxazin, flumipropyn,flupropacil, fluthiacet-methyl, pyrazoxyfen, sulfentrazone,thidiazimine, carfentrazone, azafenidin;

c31: pyrazoles: nipyraclofen;

c32: pyridazines: chloridazon, maleic hydrazide, norflurazon, pyridate;

c33: pyridinecarboxylic acids: clopyralid, dithiopyr, picloram,thiazopyr;

c34: pyrimidyl ethers: pyrithiobac-acid, pyrithiobac-sodium,pyriminobac-methyl, bispyribenzoxim, bispyribac-sodium;

c35: sulfonamides: flumetsulam, metosulam, cloransulam-methyl,diclosulam;

c36: triazines: ametryn, atrazine, aziprotryn, cyanazine, cyprazine,desmetryn, dimethamethryn, dipropetryn, eglinazine-ethyl, hexazinon,procyazine, prometon, prometryn, propazin, secbumeton, simazine,simetryn, terbumeton, terbutryn, terbuthylazine, trietazine, dimesyflam;

c37: triazinones: ethiozin, metamitron, metribuzin;

c38: triazolecarboxamides: triazofenamid;

c39: uracils: bromacil, lenacil, terbacil;

c40: various: benazolin, benfuresate, bensulide, benzofluor, butamifos,cafenstrole, chlorthal-dimethyl (DCPA), cinmethylin, dichlobenil,endothal, fluorbentranil, mefluidide, perfluidone, piperophos,diflufenzopyr, diflufenzopyr-sodium

or the environmentally compatible salts of the abovementioned groups ofactive ingredients.

Examples of other preferred active ingredients c) are bromobutide,dimethenamide, isoxaben, propanil, glufosinate-ammonium, glyphosate,sulfosate, mefenacet, thiafluamide, 2,4-D, 2,4-DB, dichlorprop,dichlorprop-P, dichlorprop-P(2,4-DP-P), fluoroxopyr, MCPA, mecoprop,mecoprop-P, dicamba, bentazone, clomazone, diflufenican, sulcotrione,isoxaflutole, phenmedipham, thiobencarb, quinclorac, quinmerac,acetochlor, alachlor, butachlor, metazachlor, metolachlor, pretilachlor,butroxydim, caloxydim, clethodim, cycloxydim, sethoxydim, tralkoxydim,2-{1-[2-(4-chlorophenoxy)propyloxyimino]-butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one,pendimethalin, acifluorfen-sodium, bifenox, fluoroglycofen-ethyl,fomesafen, lactofen, chlortoluron, cycluron, dymron, isoproturon,methabenzthiazuron, imazaquin, imazamox, imazethabenz-methyl,imazethapyr, bromoxynil, ioxynil, clodinafop, cyhlaofop-butyl,fenoxyprop-ethyl, fenoxaprop-p-ethyl, haloxyfop-p-methyl, cinidon-ethyl,flumiclorac-pentyl, carfentrazone, flumipropyn, fluthiacet-methyl,pyridate, clopyralid, bispyribac-sodium, pyriminobac-methyl,flumetsulam, metosulam, atrazine, cyanazine, terbutylazine, benazolin,benfuresate, cafenstrole, cinemthylin, ammonium-bentazon, cloquintocet,diflufenzopyr, diflufenzopyr-sodium, pyraflufen-ethyl.

Particularly preferred are the following compounds c): 2,4-D,dichlorprop-P, MCPA, mecoprop-P, dicamba, bentazone, diflufenican,sulcotrione, quinclorac, caloxydim, cycloxydim, sethoxydim,2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one, acifluorfen-sodium,fluoroglycofen-ethyl, bromoxynil, fenoxyprop-ethyl, cinidon-ethyl,atrazine, terbutylazine, ammonium-bentazone, cloquintocet, thiafluamid,isoxaflutole, diflufenzopyr, diflufenzopyr-sodium, carfentrazone,imazamox.

Very especially preferred are the following compounds c): 2,4-D,dichlorprop-P, mecoprop-P, MCPA, ammonium-bentazone, bentazone,diflufenican, quinclorac,2-{1-[2-(4-chlorophenoxy)propyloxyimino]butyl}-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1-one, caloxydim, cycloxydim,sethoxydim, fluoroglycofen-ethyl, cinidon-ethyl, atrazine,terbutylazine, dicamba, diflufenzopyr and diflufenzopyr-sodium.

If any other active ingredients c) are present, they generally amount tofrom 0.5 to 75, preferably 1 to 60,% by weight of the formulation.

The solid mixtures according to the invention may additionally compriseformulation auxiliaries which are known per se in addition to theabove-described components a), b) and c).

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts or ammonium salts of aromatic sulfonic acids, e.g. ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fattyacids, alkyl polyglycosides, condensates of sulfonated naphthalene andits derivatives with formaldehyde, condensates of naphthalene or of thenaphthalenesulfonic acids with phenol and formaldehyde, condensates ofphenol or of phenolsulfonic acid with formaldehyde, condensates ofphenol with formaldehyde and sodium sulfite, polyoxyethylene octylphenylether, ethoxylated isooctyl-, octyl- or nonylphenol, tributylphenylpolyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol,fatty alcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated triarylphenols, salts ofphosphated triarylphenol ethoxylates, polyoxypropylene alkyl ethers,lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfitewaste liquors or methylcellulose or mixtures of these.

When surface-active substances are used concomitantly, they generallyamount to from 0.5 to 25% by weight, based on the total weight of thesolid mixture.

The solid mixtures according to the invention can also be used togetherwith carrier materials. Examples of carriers which may be mentioned are:

mineral earths such as silicas, silica gels, silicates, talc, kaolin,attaclay, limestone, chalk, loess, clay, dolomite, diatomaceous earth,calcium sulfate, magnesium sulfate, magnesium oxide, ground syntheticmaterials, fertilizers such as ammonium sulfate, ammonium phosphate,ammonium nitrate, thiourea and urea, products of vegetable origin suchas cereal meals, tree bark meal, wood meal and nutshell meal, cellulosepowders, attapulgites, montmorillonites, mica, vermiculites, syntheticsilicas and synthetic calcium silicates or mixtures of these.

The following may be employed as other additives in amounts which arecustomary per se:

Water-soluble compounds or salts such as:

sodium sulfate, pottasium sulfate, sodium chloride, potassium chloride,sodium acetate, ammonium hydrogen sulfate, ammonium chloride, ammoniumacetate, ammonium formate, ammonium oxalate, ammonium carbonate,ammonium hydrogen carbonate, ammonium thiosulfate, ammonium hydrogendiphosphate, ammonium dihydrogen monophosphate, ammonium sodium hydrogenphosphate, ammonium thiocyanate, ammonium sulfamate or ammoniumcarbamate;

binders such as:

polyvinylpyrrolidone, polyvinyl alcohol, partially hydrolyzed polyvinylacetate, carboxymethylcellulose, starch, vinylpyrrolidone/vinyl acetatecopolymers and polyvinyl acetate or mixtures of these;

lubricants such as:

magenesium stearate, sodium stearate, talc or polyethylene glycol ormixtures of these;

antifoams such as:

silicone emulsions, long-chain alcohols, phosphoric esters, acetylenediols, fatty acids or organofluorine compounds, and

complexing agents such as:

salts of ethylenediaminetetraacetic acid (EDTA), salts oftrinitrilotriacetic acid or salts of polyphosphoric acids, or mixturesof these.

The solid mixtures according to the invention can be prepared in theform of powders, granules, briquettes, tablets and similar formulationvariants. In addition to powders, granules are especially preferred. Thepowders may be water-soluble or water-dispersible powders. The granulesmay be water-soluble or water-dispersible granules for use in sprayapplication, or so-called spreading granules for direct application. Themean particle size of the granules is generally between 200 μm and 2 mm.

The resulting granule formulations are dust-free, free-flowing productswhich do not cake and are readily soluble or dispersible in cold water.

Due to their characteristics, the products can be readily packaged inrelatively large amounts. In addition to containers such as polymer,paper or laminated sacks or bags, the products can be handled incardboard boxes or other containers. To avoid further exposure of theuser, it is possible to package the products in water-soluble film bags,for example polyvinyl alcohol film bags, which are introduced directlyinto the spray tank, where they dissolve. Substances which can beemployed for such water-soluble films are, inter alia, polyvinyl alcoholor cellulose derivatives such as methylcellulose,methylhydroxypropylcellulose or carboxymethylcellulose. Since theproduct is packaged in portions which are the right size for use, theuser no longer comes into contact with it. The water-soluble bags arepreferably packaged in an external sheath which is impermeable to watervapor, such as polyethylene film, polyethylene laminated paper oraluminum foil.

The solid formulations according to the invention can be prepared byvarious processes known to those skilled in the art.

A Preferred preparation processes for the abovementioned formulationswhich may be mentioned are extruder granulation, spray drying,fluidized-bed agglomeration, mixer granulation and disk granulation.

Fluidized-bed granulation (FBG) is especially suitable. Depending on thedesired composition of the formulation, an aqueous solution, emulsion orsuspension which comprises all product components is sprayed andagglomerated in an FBG apparatus.

However, it is also possible, if desired, to introduce active ingredientsalts and/or inorganic ammonium salts into the apparatus and to spraythem with a solution or emulsion/suspension of the remaining productconstituents, during which process agglomerates are formed. It isfurthermore possible to apply aqueous solutions, emulsions orsuspensions which comprise specific product constituents to activeingredient granules, an active ingredient salt and/or an inorganicammonium salt in succession, thus obtaining a variety of coating layers.

In general, the granules are dried sufficiently in the course of thefluidized-bed granulation process. However, it may be advantageous toproduce a separate drying step after granulation, either in the same, orin a separate, dryer. After granulation/drying, the product is cooledand screened.

A further especially suitable process is extruder granulation. Suitablefor extruder granulation are preferably basket, radial or dome extrudersin which the granule kernel is subjected to a low degree of compaction.

To carry out the granulation, a mixture of solid substances is made intoa paste with a granulation liquid in a suitable mixer until anextrudable mass is formed. This is extruded in one of the abovementionedextruders. To carry out the extrusion, apertures of dimensions between0.3 and 3 mm are used (preferably 0.5-1.5 mm). Mixtures of solids whichare used are mixtures of active ingredients, formulation auxiliariesand, if appropriate, water-soluble salts. These are generallypre-ground. In some cases, it suffices only to pre-grind, in suitablemills, those substances which are water-insoluble.

Suitable granulation liquids are water, the sulfate- orsulfonate-containing surfactants according to the invention or aqueoussolutions of these. Also suitable are aqueous solutions of inorganicsalts, non-ionic surfactants, anionic surfactants, solutions of binderssuch as polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose,starch, vinylpyrrolidine/vinyl acetate copolymers, sugars, dextrin orpolyethylene glycol. After extruder granulation, the resulting granulesare dried and, if appropriate, screened in order to remove coarseparticles and fines.

Comparison Example 1

A premix composed of:

73.1 g of SU 1 (compound No. 47 of Table 1) (technical grade, 95.7%),  8 g of Tamol ® NH and 17.9 g of Ufoxane ® 3A

was mixed and ground in a high-speed rotor mill.

Also,

 7.1 g of premix,   5 g of Extrusil ® (Degussa) and 77.9 g of ammoniumsulfate

were mixed with 24 g of Klearfac^(R) AA-270 as a 50% aqueous solution ina Moulinette kitchen blender. The resulting mass was extruded by meansof an extruder (KAR-75, Fitzpatrick Europe). The resulting moistgranules were dried in a drying oven.

Comparison Example 2

A premix composed of:

73.1 g of SU 1 (technical grade, 95.7%)   8 g of Tamol ® NH and 17.9 gof Ufoxane ® 3A

was mixed and ground in a high-speed rotor mill.

Also,

 7.1 g of premix,   15 g of Extrusil ® (Degussa) and 77.9 g of ammoniumsulfate

were mixed with 23 g of Armoblem^(R) 557 as a 50% aqueous solution in aMoulinette kitchen blender. The resulting mass was extruded by means ofan extruder (KAR-75, Fitzpatrick Europe). The resulting moist granuleswere dried in a drying oven.

Comparison Example 3

A premix composed of:

73.1 g of SU 1 (technical grade, 95.7%),   8 g of Tamol ® NH and 17.9 gof Ufoxane ® 3A

was mixed and ground in a high-speed rotor mill.

Also,

 7.1 g of premix,   15 g of Extrusil ® (Degussa) and 77.9 g of ammoniumsulfate

were mixed with 29 g of Lutensol^(R) ON 80 as a 50% aqueous solution ina Moulinette kitchen blender. The resulting mass was extruded by meansof an extruder (KAR-75, Fitzpatrick Europe). The resulting moistgranules were dried in a drying oven.

Comparison Example 4

A mixture composed of:

 6.9 g of metsulfuron-methyl (technical grade, 99%)   3 g of Tamol ® NH  6 g of Ufoxane ® 3A   15 g of Extrusil ® and 43.1 g of ammoniumsulfate

was mixed thoroughly and ground by means of a laboratory high-speedrotor mill. The resulting powder mixture was mixed with 17 parts ofLutensol^(R) ON 30 in a planetary paddle mixer (Kenwood Chef). Theresulting mass was extruded by means of an extruder (DGL-1, FitzpatrickEurope). The resulting moist granules were dried in a fluidized-beddryer.

EXAMPLE 1

A premix composed of:

73.1 g of SU 1 (technical grade, 95.7%)   8 g of Tamol ® NH and 17.9 gof Ufoxane ® 3A

was mixed and ground in a high-speed rotor mill.

Also,

 7.1 g of premix,   5 g of Tamol ® NH, 58.9 g of ammonium sulfate,   3 gof Sipernat ® 22,   25 g of Lutensit ® A-LBN and   1 g of antifoamemulsion SRE

were made into a paste with 14 ml of water in a Moulinette kitchenblender. The resulting mass was extruded by means of an extruder(KAR-75, Fitzpatrick Europe). The resulting moist granules were dried ina drying oven.

EXAMPLE 2

A premix composed of:

73.1 g of SU 1, technical grade, 17.9 g of Ufoxane ® 3A and   8 g ofTamol ® NH

was mixed and ground in a high-speed rotor mill.

Also,

 7.1 g of premix,   15 g of Extrusil ®, 52.9 g of ammonium sulfate and  25 g of Lutensit ® A-PS

were made into a paste with 14 ml of water in a Moulinette kitchenblender. The resulting mass was extruded by means of an extruder(KAR-75, Fitzpatrick Europe). The resulting moist granules were dried ina drying oven.

EXAMPLE 3

A premix composed of:

73.1 g of SU 1 (technical grade, 95.7%)   8 g of Tamol ® NH and 17.9 gof Ufoxane ® 3A

was mixed and ground in a high-speed rotor mill.

Also,

7.1 g of premix, 15 g of Extrusil^(R) (Degussa), 52.9 g of potassiumsulfate and 24 g of Lutensit^(R) AP-S

were mixed in a Moulinette kitchen blender. The resulting mass wasextruded by means of an extruder (KAR-75, Fitzpatrick Europe). Theresulting moist granules were dried in a drying oven.

EXAMPLE 4

A mixture composed of:

5.1 g of SU 1 (technical grade, 98.54%) 3 g of Tamol^(R) NH 6 g ofUfoxane^(R) 3A 15 g of Extrusil^(R) (Degussa) and 44.9 g of ammoniumsulfate

was mixed and ground in a high-speed rotor mill.

In a Moulinette kitchen blender, the resulting powder was mixed with 25g of Witconate^(R) 3203 and 1 g of antifoam SRE. The resulting mass wasextruded by means of an extruder (KAR-75, Fitzpatrick Europe). Theresulting moist granules were dried in a drying oven.

EXAMPLE 5

A mixture composed of:

5.1 g of SU 1 (technical grade, 98.54%) 3 g of Tamol^(R) NH 6 g ofUfoxane^(R) 3A 15 g of Extrusil^(R) (Degussa) and 44.9 g of ammoniumsulfate

was mixed and ground in a high-speed rotor mill. In a Moulinette kitchenblender, the resulting powder was mixed with 25 g of Witconate^(R) NAS 8and 1 g of antifoam SRE. The resulting mass was extruded by means of anextruder (KAR-75, Fitzpatrick Europe). The resulting moist granules weredried in a drying oven.

EXAMPLE 6

A premix composed of:

5.1 g of SU 1 (technical grade, 98.5%) 3.1 g of cinidon-ethyl (technicalgrade, 98%) 1 g of Tamol^(R) NH 2 g of Ufoxane^(R) 3A 15 g ofExtrusil^(R) (Degussa) and 47.8 g of ammonium sulfate

was mixed and ground in a jet mill.

Also,

74 g of premix, 25 g of Lutensit^(R) APS (alkylsulfonate, BASF AG,technical grade, 65%) and 1 g of antifoam SRE

were mixed in a planetary paddle mixer (Kenwood Chef), and a total of6.5 g of water (based on 100 g of product) was added. The resulting masswas extruded by means of an extruder (DGL-1, Fitzpatrick Europe). Theresulting moist granules were dried in a fluidized-bed dryer. This gavereadily dispersible granules.

EXAMPLE 7

A premix composed of:

5.1 g of SU 1 (technical grade, 98.5%) 3.1 g of cinidon-ethyl (technicalgrade, 98%) 1 g of Tamol^(R) NH 2 g of Ufoxane^(R) 3A 15 g ofExtrusil^(R) (Degussa) and 47.8 g of ammonium sulfate

was mixed and ground in a jet mill.

Also,

74 g of premix, 22.5 g of Lutensit^(R) APS (alkylsulfonate, BASF AG,technical grade, 65%) and 1 g of antifoam SRE

were mixed in a planetary paddle mixer (Kenwood Chef), and a total of 5g of water (based on 100 g of product) was added. The resulting mass wasextruded by means of an extruder (DGL-1, Fitzpatrick Europe). Theresulting moist granules were dried in a fluidized-bed dryer. This gavereadily dispersible granules.

EXAMPLE 8

A premix composed of:

6 g of SU 1 10 g of clefoxydim-lithium 10 g of Extrusil^(R) 10 g of urea3 g of Morwet^(R) EFW 1 g of Aerosol^(R) TO B and 40 g of Tamol^(R) NH

was mixed thoroughly and ground by means of an air-jet mill. Theresulting powder mixture was mixed with 20 parts of Lutensit^(R) APS ina planetary paddle mixer (Kenwood Chef). To produce an extrudable mass,1.8% of water was also added. The resulting mass was extruded by meansof an extruder (DGL-1, Fitzpatrick Europe). The resulting moist granuleswere dried in a fluidized-bed dryer.

EXAMPLE 9

A mixture composed of:

6.9 g of metsulfuron-methyl (technical grade, 99%) 3 g of Tamol^(R) NH,6 g of Ufoxane^(R) 3A, 15 g of Extrusil^(R) and 43.1 g of ammoniumsulfate

was mixed thoroughly and ground by means of a laboratory high-speedrotor mill. The resulting powder mixture was mixed with 25 parts ofLutensit^(R) APS in a planetary paddle mixer (Kenwood Chef). Theresulting mass was extruded by means of an extruder (DGL-1, FitzpatrickEurope). The resulting moist granules were dried in a fluidized-beddryer.

The table which follows illustrates the components employed in theexamples:

TABLE 2 Name Chemical name Manufacturer Tamol ® NH NaphthalenesulfonicBASF AG acid/formaldehyde condensate Ufoxane ® 3A Sodium ligno-Borregaard sulfonate Morwet ® D425 Naphthalenesulfonic BASF AGacid/formaldehyde condensate Wettol ® NT 1 Alkylnaphthalene- BASF AGsulfonate Extrusil ® Highly disperse Degussa calcium silicate Sipernat ®22 Highly disperse Degussa silica Antischaummittel SRE Silicone oilWacker-Chemie emulsion Lutensol ® ON 30 Fatty alcohol BASF AG ethoxylate(3EO) Lutensol ® ON 60 Fatty alcohol BASF AG ethoxylate (6EO) Lutensol ®ON 80 Fatty alcohol BASF AG ethoxylate (8EO) Lutensit ® A-PS Sodiumalkane- BASF AG sulfonate Lutensit ® A-LBN Sodium alkylbenzene- BASF AGsulfonate Armoblem ® 557 Ethoxylated fatty Akzo amine Klearfac ® AA-270Phosphated fatty BASF Corporation alcohol ethoxylate Morwet ® EFWAnionic wetter blend Witco Witconate 3203 Sodium alpha-olefin- Witcosulfonate Witconate NAS 8 Sodium alkane- Witco sulfonate Aerosol OT-BSodium dioctylsulfo- American Cyanamid succinate SU 1 Comp. 47 of Table1 Clefoxydim 2-{1-[2-(4-chloro- phenoxy)propyloxya- mino]butyl}-5-tetra-hydrothiopyran-3-yl- cyclohexane- 1,3-dione Cinidon-ethyl ethyl(Z)-2-chloro- 3-[2-chloro-5- (4,5,6,7-tetra- hydro-1,3-dioxoiso-indoledion-2-yl)- phenyl]acrylate

Test Methods

The active ingredient content of SU of the formulations given in theabove examples was determined in each case by means of quantitative HPLCand is given in Table 3 in per cent.

Storage Stability Tests

To test for storage stability, samples of the formulation in question asdescribed in Examples 1-9 and Comparison Examples 1 to 4 were stored fora specified time (14 days or 42 days) in tightly sealed glass containersat the temperature indicated (40° C., 50° C. or 54° C.). The samples arethen examined and compared with the comparison value at the beginning ofthe storage period (zero value). The active ingredient content is givenas relative SU content, based on the zero value (in per cent). Thestorage tests were carried out by a method similar to CIPAC MT 46. Thelong-term stability of a product is estimated on the basis of short-termstorage at elevated temperature.

Table 3 shows the results from the determination of the storagestability of the solid mixtures prepared as shown in Examples 1-9 andcomparison Examples 1-4.

The results demonstrate the superior characteristics of the solidmixtures according to the invention.

TABLE 3 Relative active Active ingredient ingredient content Ex.content, in % by of SU after 14 No. Adjuvant weight days, 54° C. C1Klearfac ® AA-270 4.3  0 C2 Armoblem ® 557 3.9 13 C3 Lutensit ® ON 603.2 14 C4 Lutensol ® ON 30 7.3 48 1 Lutensit ® A-LBN 5 90 2 Lutensit ®A-PS 5.1 88 3 Lutensit ® A-PS 5.5 100  4 Witconate ® 3203 5.5 93 5Witconate ® NAS 8 5.6 90 6 Lutensit ® A-PS 5.38 95 7 Lutensit ® A-PS5.57  94¹ 8 Lutensit ® A-PS 6.4 100  9 Lutensit ® A-PS 7.3 69 ¹measuredafter storage for 30 days at 50° C.

We claim:
 1. A solid mixture comprising a) a sulfonylurea of the formulaIII

 where the substituents have the following meanings: R¹ is C₁-C₄-alkylwhich can have attached to it one to five of the following groups:methoxy, ethoxy, SO₂CH₃, cyano, chlorine, fluorine, SCH₃, S(O)CH₃;halogen; a group ER¹⁹ where E is O, S or NR²⁰; COOR¹²; NO₂; S(O)_(n)R¹⁷,SO₂NR¹⁵R¹⁶, CONR¹³R¹⁴; R² is hydrogen, methyl, halogen, methoxy, nitro,cyano, trifluoromethyl, trifluoromethoxy, difluoromethoxy or methylthio,Y is F, CF₃, CF₂Cl, CF₂H, OCF₃, OCF₂Cl, C₁-C₄-alkyl or C₁-C₄-alkoxy; Xis C₁-C₂-alkoxy, C₁-C₂-alkyl, C₁-C₂-alkylthio, C₁-C₂-alkylamino,di-C₁-C₂-alkylamino, halogen, C₁-C₂-haloalkyl, C₁-C₂-haloalkoxy, R ishydrogen or methyl; R¹⁹ is C₁-C₄-alkyl; C₂-C₄-alkenyl, C₂-C₄-alkynyl orC₃-C₆-cycloalkyl, which can have attached to them 1 to 5 halogen atoms;furthermore, in the event that E is O or NR²⁰, R¹⁹ is alsomethylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, allylsulfonyl,propargylsulfonyl or dimethylsulfamoyl; R²⁰ is hydrogen, methyl orethyl; R¹² is a C₁-C₄-alkyl group, which can have attached to it up tothree of the following radicals: halogen, C₁-C₄-alkoxy, allyl orpropargyl; R¹⁷ is a C₁-C₄-alkyl group, which can have attached to it oneto three of the following radicals: halogen, C₁-C₄-alkoxy, allyl orpropargyl; R¹⁵ is hydrogen, a C₁-C₂-alkoxy group or a C₁-C₄-alkyl group;R¹⁶ is hydrogen or a C₁-C₄-alkyl group; n is 1-2 and Z is N or CH and b)an alkyl sulfonate-containing surfactant.
 2. A solid mixture as claimedin claim 1, comprising a further herbicidally active ingredient.
 3. Asolid mixture as claimed in claim 1, comprising 0.5 to 75% by weight ofcomponent a).
 4. A solid mixture as claimed in claim 1, comprising 1 to50% by weight of component b).
 5. A method of controlling undesiredvegetation, which comprises treating the plants and/or the area to bekept free of the plants with a herbicidally active amount of a solidmixture as claimed in claim
 1. 6. A process for the preparation ofherbicide formulations, which comprises mixing a sulfonylurea of theformula III with a sulfonate-containing surfactant to obtain a solidmixture as claimed in claim
 1. 7. A solid mixture as claimed in claim 4,comprising 5 to 25% by weight of component b).